Lube oil hydrocracking with zsm-5 zeolite

ABSTRACT

A process for preparing lube oils characterized by possessing low pour points is set forth. The process involves subjecting a lube stock to a hydrocracking operation utilizing a catalyst mixture comprising hydrogenation components, a conventional cracking catalyst which can be either crystalline or amorphous and a crystalline aluminosilicate of the ZSM-5 type.

United States Patent 1 Orkin [4 Aug. 28, 1973 LUBE 01L HYDROCRACKINGWITH zsM-s 3,494,854 2/1970' Gallagher et al. 208/59 ZEOLITE 3,620,963 11/197] Mulaskey 208/1 1 1 3,650,945 3/1972 Bertolacini et al. 208/1 1 IBernard A. Orkin, Cherry Hill, NJ.

Mobil Oil Corporation, New York, NY.

Filed: Mar. 17, 1971 Appl. No.: 125,409

Inventor:

Assignee:

US. Cl 208/111, 208/18, 252/455 Z Int. Cl C10g 13/02, ClOg 37/02 Fieldof Search 208/1 1 l, 18

References Cited UNITED STATES PATENTS 4/1969 Morris et al. 208/8711/1970 Morris et al. 208/111 [57] ABSTRACT A process for preparing lubeoils characterized by possessing low pour points is set forth. Theprocess involves subjecting a lube stock to a hydrocracking operationutilizing a catalyst mixture comprising hydrogenation components, aconventional cracking catalyst which can be either crystalline oramorphous and a crystalline aluminosilicate of the ZSM-5 type.

9 Claims, No Drawings" LUBE OIL IIYDROCRACKING WITH ZSM-S ZEOLITEBACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to the production of lube oils of high VI and low pour points bya completely catalytic process so that solvent dewaxing can beeliminated. The above is accomplished by using a hydrocracking catalystwhich contains a mixture of at least two acidic components one acidiccomponent being a conventional cracking catalyst, e.g. silica-alumina,or a large pore zeolite such as X or Y or mixtures thereof and the otheracidic component being a crystalline aluminosilicate zeolite of theZSM-5 type. A hydrogenation/dehydrogenation component is also presenteither as separate discrete particles or associated with either or bothof the acidic components by conventional techniques such as baseexchange or impregnation.

2. Description of the prior Art It is well known in the art to formvarious lubricatin oils commonly referred to as lubes from hydrocarbonfractions derived from petroleum crudes. A heretofore practiced commonprocedure known in the art is to extract these hydrocarbon fractionswith variousselective solvents for aromatic compounds so as to obtainaraffinate of a desired high visocity index, such material beingresistant to changes in viscosity with changes in temperature and thusbeing useful under various operating conditions. Moreover, it is.particularly desired that the lube oil have a low pour point so that itcan be effectively used at low temperature conditions since formation ofwax'crystals at low temperatures clogs strainers and'inhibitscirculation of the lubricant. This has generally been accomplished bysolvent dewaxing at low temperature with solvent mixtures such as ketoneplus benzene. The heretofore practiced conventioinai solvent extractionprocesses plus solvent dewax ing'; although accepted commercially,nevertheless, sufferfrdin' the disadvantage that the combination isrelatively expensive to operate.

It has been shown that high VI lube stocks can be prepared from rawdistillates and residual oils by a mild hydrocracking adequate to openaromatic ring structures without excessive conversion to naphtha andlight gaseous hydrocarbons. The resultant products often have Vlhigherthan solvent refined oils .from the same source, but still requiredewaxing for acceptable pour point. =Solvent dewaxing is the acceptedoperation, since it will remove both paraffin wax'and microcrystallinewax. 4

Recently proposals have been made to accomplish dewaxing in a catalyticoperation by contact with .a shape selective cracking of hydrocrackingcatalyst. Such materials as zeolite A and erionite will not accept theslightly branched chain compounds of microcrystalline wax. Due to theirgreat size, parafi'in wax (straight chains of v24 carbon atoms) areadmitted slowly, if at all. Mordenite tends to coke up and becomeinoperative during relatively short time on stream.

In an attempt to overcome the inherent difficulties when employing acrystalline aluminosilicate having a pore size of five Angstrom unitsfor catalystic dewaxing, the prior art resorted to so-called combinationprocesses wherein'dewaxing was carried out utilizing both solventtechniques and catalytic conversion. In pro- 20, 1970, now abandoned, aprocess is disclosed for the production of lube stocks utilizing acatalyst of the ZSM-S type. In said copending application, a lube stockis first subjected to mild solvent dewaxing followed by catalyticconversion over a ZSM-S type catalyst. Although the process disclosed inthis application represents a significant advance over the-heretoforepracticed processes with respect to the quality of wax which is producedand the yields which are obtained, nevertheless, it is still necessaryto use both solvent dewaxing and catalytic conversion thereby sufferingthe disadvantage of the use of multiple reactors.

DESCRIPTION OF THE INVENTION It has now been found that improved resultscan be obtained in the catalytic hydrocracking of lube stocks to producelube oils having high viscosity indexes and .low pour points bycontacting said lube stock iinthe presence of hydrogen with a catalystmixture which comprises a hydrogenation component and atileast twoseparate acidic'cracking-catalysts, one being a-conven} tional crackingcatalyst of the large pore and the other being a crystallinealuminosi'licate of the ZSM-S type. As .is more fully set forth incopending application Ser. No. 56,652 the ZSM-S type zeolites which areused in combinationwith the large pore cracking cata ,=lysts cangenerally be started to possess a pore size which will :alow entry intotheir internal pore structure of normal aliphatic compounds :andslightly branched aliphatic compounds, particuladymonome'thylsubstituted compounds, yet substantially exclude allcompounds containing at least a quaternary carbon atom or compoundshaving a molecular dimension equal to or substantially greater than aquaternary carbon atom. Thus, ZSM-5 type crystalline aluminosilicateshave pore sizes which are larger than the conventional 5 Angstrom type'aluminosilicates andyet smaller than the large pore sizealuminosilicates such as those of the faujasite family. I r

The second acidiccomponent employed .in the novel catalyst mixtures ofthis .invention is :a conventional large pore cracking catalystsuchaswsilica-a'lumina, .silif ca-titania, .silica-zirconia, silica-boria,clay, .or a large pore 'aluminosilicate of the X and Y type of any mix-,tures thereof. These'materials, as isgenerally known in the art, havepore sizes such that :they will allow entry of essentially all thecomponents present in a lube stock.

While not :wishing'ito abe bound'by .any theoryof operation,nevertheless, .itappears that conventional acidic" component of-thehydrocrackingcatalyst hydrogenates and opens ring compounds which havelow VI "whereas also appear "likely that :there is .a synergistic effectdue to a mutual coaction of each acidic .component not only witheachother butalsowith-rthezfeedmaterial. In

.any event, irrespective of anytheoreticalconsideration as to why :thecatalyst :system operates, it has been found that such a catalyst systemresults in the production of acceptable lubes from raw distillates andresiduals by a completely catalytic process without necessitatingsolvent dewaxing.

The ZSM-S type zeolite utilized in the novel process of this inventionhas the characteristic x-ray diffraction pattern set forth in Table l,hereinbelow. ZSM-S compositions can also be identified, in terms of moleratios of oxides, as follows:

0.9: 0.2 M ln O W -100 YO, 2 H O wherein M is a cation, n is the valenceof said cation, W is selected from the group consisting of aluminum andgallium, Y is selected from the group consisting of silicon andgermanium, and z is from 0 to 40. In a preferred synthesized form, thezeolite has a fomiula, in terms of mole ratios of oxides, as follows:

0.9 i 0.2 M /n O A1 0 5-100 SiO, 1 H 0 and M is selected from the groupconsisting of a mixture of alkali metal cations, especially sodium, andtetraalkylammonium cations, the alkyl groups of which preferably containto carbon atoms.

In a preferred embodiment of ZSM5, W is aluminum, Y is silicon and thesilica/alumina mole ratio is at least and ranges up to about 60.

Members of the family of ZSM-5 zeolites possess a definitedistinguishing crystalline structure whose x-ray diffraction patternshows the following significant lines:

These values as well as all other x-ray data were determined by standardtechniqes. The radiation was the K-a1pl1adoublet of copper, and ascintallation counter spectrometer with a strip chart pen recorder wasused. The peak'heights, I, and the positions as a function of two timestheta, where theta is the Bragg angle, were read from the spectrometerchart. From these the relative intensities, 100 l/I, where I is theintensity of the strongest line or peak, and d(obs), the interplanarspacing in A, corresponding to the recorded lines, were calculated. InTable 1 the relative intensities are given in terms of the symbols Sstrong, M= medium, MS medium strong, MW medium weak and VS= very strong.It should be understood that this x-ray diffraction pattern ischaracteristic of all the species of ZSM-5 compositions. Ion exchange ofthe sodium ion with cations reveals substantially the same pattern withsome minor shifts in interplanar spacing and variation in relativeintensity. Other minor variations can occur depending on the silicon toaluminum ratio of the particular sample, as well as if it has beensubjected to thermal treatment.

ZSM-5 is disclosed and claimed in copen'ding application Ser. No.865,472, filed Oct. 10, 1969.

Another operable zeolite falling within the above class is zeolite ZSM-8which is described and claimed in Ser. No. 865,418, filed October 10,1969.

ZSM-8 can also be identified, in terms of the mole ratios of oxides, asfollows:

0.9 i 0.2 M O Ai,o,= 5-100 sio 2 H O wherein M is at least one cation, nis the valence thereof and z is from 0 to 40. In a preferred synthesizedform, the zeolite has a formula, in terms of mole ratios of oxides asfollows: I

0.9 i 0.2 M,,,,O A1,O 10-60 SiO, 2 H O and M is selected from the groupconsisting of a mixture of alkali metal cations, especially sodium, andtetraethylammonium cations.

The ZSM-S type zeolites used in the instant invention usually have theoriginal cations associated therewith replaced by a wide variety ofother cations according to techniques well known in the art. Typicalreplacing cations would include hydrogen, ammonium and metal cationsincluding mixtures of the same. Of the replacing metallic cations,particular preference is given to cations of ammonium, hydrogen, rareearth, mg, Zn, Mn, Al CA, and mixtures thereof.

Typical ion exchange techniques would be to contact the particularzeolite with a salt of the desired replacing cation or cations. Althougha wide variety of salts can be employed, particular preference is givento chlorides, nitrates and sulfates.

Representative ion exchange techniques are disclosed in a wide varietyof patents including US. Pat Nos. 3,140,249: 3,140,251; and 3,140,253.

Following contact with the salt solution of the desired replacingcation, the zeolites may be washed with water and dried at a temperatureranging from 15 0F to about 600F and thereafter heated in air or otherinert gas at temperatures ranging from about 500F to 1500F for periodsof time ranging from 0.1 to 48 hours or more.

As had heretofore been pointed out in one embodiment, the novel catalystcomposites of this invention comprise a physical mixture of at least twodifierent cracking components, a ZSM5 type zeolite and a conventibnallarge pore cracking catalyst. In one embodiment, a mixture of catalystparticles is used in which each particle contains only one of the twotypes of cracking components. Thus, for example, a mixture of particlesof ZSM-5 type crystals and particles comprising silica-alumina may becomposited in a hydrocracking catalyst. Ai hydrogenation/dehydrogenationcomponent is present in both cracking components. Alternatively, thecatalyst components may be pelleted, cast, molded, spray-dried, orotherwise formed into pieces of desired size and shape such as rods,spheres, pellets, etc.

The large pore size conventional cracking catalyst includes inorganicoxides. Of these, inorganic oxides such as clay, chemically treatedclay, silica, silicaalumina, etc. are particularly preferred because oftheir superior porosity, and stabilityunder a reaction conditions,especially those reaction conditions encountered in the hydrocracking oflube stocks.

The compositng of the ZSM-S type zeolite with an inorganic oxidecracking catalyst can be achieved by several methods wherein thealuminosilicates are reduced to a particle size less than 40 microns,preferably less than 10 microns, and intimately admixed with aninorganic oxide while the latter is in a hydrous state such as in theform of hydrosol, hydrogel, wet gelatinous precipitate, or in a driedstate. or a mixture thereof. Thus, finely divided ZSM-S typealuminosilicates can be mixed directly with a siliceous gel formed byhydrolyzing a basic solution of alkali metal silicate with an acid suchas hydrochloric, sulfuric, acetic, etc. The mixing of the threecomponents can be accomplished in any desired manner, such as inballmill or other types of mills. The aluminosilicates also may bedispersed in a hydrosol obtained by reacting an alkali rnetal silicatewith an acid or alkaline coagulant. The hydrosol is then permitted toset in mass to a hydrogel sphere consisting of stream and air or a gaswhich isnot which. is thereafter dried and broken into pieces of desiredshape or dried by conventional spray drying techniqes or dispersedthrough anozzle into a bath of oil or other water-immiscible suspendingmedium to obtain spheroidally shaped bead particles of catalyst such asdescribed in US. Pat. No. 2,384,946. The aluminosilicate siliceous gelthus obtained is washed free of soluble salts an thereafter dried and/orcalcined as desired.

combinations thereof. The preparation of plural gels is a clay mineralwhichhasbeen treated with anacid medium to render it active. Thealuminosilicate can be incorporated into the clay simply by blending thetwo and fashioning the mixture into desired shapes. Suitable claysinclude attapulgite, kaolin, sepiolite, polygarskite,

- kaolinite, halloysite, plastic ball clays,bentonite, montmorillonite,illite, chlorite, etc. I

The catalyst product can be heated in steam or in other atmospheres,e.g., air, near the temperature contemplated for conversion but may beheated to operating temperatures initially during use in the conversionprocess. Generally, the catalyst is dried between 150F and 600F andthereafter may be calcined inair, steam, nitrogen, helium, flue gas,hydrogen or other gases not harmful to the catalyst product attemperatures ranging from about 500F to 1.,600"F for periods of timeranging from 1 .to 48-hours or more. it is to be understood that theZSM-5 aluminosilicate can also be calcined prior to incorporation intothe inorganic oxide gel cracking catalyst. It is also to be understoodthat the ZSM-S need not be ion exchanged prior to incorporation in theinorganic oxide but can be so treated during or after saidincorporation.

- The catalyst can be subjected to amild stream treatment at elevatedtemperatures of 800F'to 1,600F and preferably-at temperatures of about1,000F to 1,500F

harmful to the aluminosilicates or to the hydrogenation component. Thesteamtreatment can'be conducted before, after, or in place of thecalcination treatment. 1

The particle size of each type of cracking component 1 making up thecatalyst system is not narrowly critical but should be less thanIOOmicrons and particle sizes within the range of from less-than 0.1 to10 microns are preferred. it is also to be noted that each individualcomponent in the catalyst system need not be of the same particle size.g

The particular proportion of one component to the other in the catalystis also not narrowly critical and can vary over an extremely wide range.However, it has been found that for most purposes the weight ratio ofthe- ZSM-S type aluminosilicate to the large pore cracking catalyst canrange from 1:10 to -2:1 and preferably from 1:5 up to 2:1 and still morepreferably 1:4 to 1:1.

The ZSM-5 type crystalline aluminosilicates and the large poreconventional cracking catalyst may be added to a hydrocracking unit as amixture of crystallites withinthe-same particles of catalyst composite,-

whether the particles are beads, extrudate's, or spraydriedmicrospheres. Altemately, a mixture of particles may be added to thehydrocracking unit, some particles containing only the ZSM5 typealuminosilicate crys} tallites and hydrogenation componentand the otherparticles containing only the large pore cracking catalyst andhydrogenation component. In eithercase, the ratio of ZSM-5 typealuminosilicates to large pore cracking catalyst should bewithin therange of 1:10 to .221. I

The amount of the hydrogenation/dehydrogenation component employed isnot narrowly critical and can range from about 0.01 to about 30 weightpercent based on the entire catalyst. A variety of hydrogenationcomponents maybe combined with either or both of the cracking componentsin any feasible manner which affords intimate contact of the components,employing well known techniques suchas impregnation, coprecip itation,coge'llation, mechanical admixtureof one com-. ponent with the otherexchange and the like. The hy drogenation component can include metals,.oxides, and sulfides of metals of the Periodic Table which fall inGroup VlB including chromium, molybdenum, tungsten, and the like; GroupIIB including zinc cadmium; and Group VIII including cobalt, nickel,platinum, palladium, rhenium, rhodium and the like and cornbinations ofmetals, sulfides and oxides of metals of Group;

VB and VIII, such as nickel-tungsten-sulfide, cobalt.

oxide-molybdenum oxide and the like.

such is desired. The. treatment may be accompished in 1 an atmosphere'ofpercent steam or in an atmo- The pre-treatment before use variesdepending on the hydrogenation component present. For example; withcomponents such as nickel-tungsten and cobalt molybdenum, the catalystissulfuractivated. But with metals like platinum or palladium, ahydrogenati'on step isemployed. These techniques are well known intheartand are accomplished in a conventional-manned Although-the conventionallarge pore cracking comthe art and particular preferenceis given tofaujasites,:

both natural and synthetic, such as zeolites X and Y. Thus, oneembodiment of this invention then includes a mixture of a ZSM- typecatalyst together with zeolite X or Y wherein either or both of thealuminosilicates have a hydrogenation component associated therewith.When employing zeolites such as X and Y as the cracking component, it ispreferred to base exchange said materials with cations in order toreduce the sodium content thereof. Compositions of this type includetechniques with Compositions of this type include techniques with theirbase exchange are well known in the art and are set forth in U.S. PatNos. 3,140,249; 3,140,251; 3,140,252; and 3,140,253.

Still another embodiment of this invention resides in the use of amatrix material in conjunction with the large pore size aluminosilicateand the ZSM-S type zeolite. Thus, by way of illustration, the process ofthis invention can be carried out with a ZSM-5 type zeolite which isdispersed in a matrix such as silica-alumina into which is added a largepore crystalline aluminosilicate such as zeolite X which is alsodispersed in a matrix such as silica alumina. The hydrogenationcomponent can be present in either or both of the crystallinealumino-silicates and/or either or both of the matrices.

The novel process of this invention is carried out at temperatures ofbelow about 650 to about 1,000F, a pressure between 100 and 5000 psig,but preferably between 1250-3000 psig. The liquid hourly space velocityis generally between 0.1 and 100 and preferably between 0.5 to 20. Thehydrogen to hydrocarbon mole ratio is generally between 1 to 80 andpreferably between 4 and 40.

The feed stocks which can be treated according to the novel process ofthis invention are waxy raw distillates and residual stocks boilingabove 650F and particularly boiling between about 650F to about 1 150F.

In each of the examples (except 14) below, there is used a catalystcomposite of ZSM-5 with a silicazirconia-clay composite which had beenimpregnated with nickel and tungsten to prepare a hydrocrackingcatalyst. That material was prepared by adding 1,350 g. kaolin-clay(moisture free basis) to 34,800 g. water with stirring. This slurry wasadded 2,037 g. silica (SiO,) as sodium silicate solution and then 31.8g. kaolin-clay (moisture free basis). A solution was made up by adding49 g. sodium zirconium silicate powder (contains 224 g. ZrO, and 1 14 g.SiO,) to 4,880 g. water and then adding 418 g. H SO, as 93.2% wt.1-1,SO,

An impregnation solution was prepared by dissolving 128.6 g of ammoniummetatungstate (72.3 percent wt W) and 184.4 g nickel nitrate Ni(NO,),.611,0 in 200 cc water. This was diluted with water to 330 cc. Thesolution was then mixed with 880 g of the silica-zirconiaclay powder(91.0. percent solids). After addition of 150 cc water to make thematerial extrudable, it was extruded twice through 1/16 inch hole withroller type California Pellet Mill. The extrudate was dried 16 hours at250F and calcined in flowing air for 3 hours at 1,000F. The product hada packed density of 0.87 g/cc and crush strength averaged 15 pounds for25 pellets. Analysis showed 4 percent of nickel and 10 percent oftungsten, by weight.

The following examples will illustrate the best mode contemplated forcarrying out this invention.

EXAMPLES 1 7 1n Examples 1-7, a catalyst mixture comprising 80 cubiccentimeters of the above described nickeltungsten impregnatedsilica-zirconia-clay and 40 cubic centimeters of ZSM-5 which had beenbase exchanged with zinc and ammonium cations (ZnH/ZSM-S) were used tohydrocrack a lube stock in order to produce lubes.

The lub'e stock employed as a feed material in each of these exampleshad the following characteristics:

Gravity, APl 29.3 Pour Point, F +80 Sulfur, Wt. 0.47 Hydrogen, Wt. 13.04I(.V. at 210F, cs 4.31 Wax, Wt. 16.3 Vacuum Assay, F

IBP 652 5% 686 10% 700 30% 733 767 804 844 852 The procedure employedinvolved contacting the catalyst mixture with the charge stock at ahydrogen circulation of 8,000 SCF/bbl. Additional operating conditions,as well as the results obtained, are shown in the following table. 1

Pour

650 F.+, Pressure Temp., wt. point, KV at KV at Example (p.s.i.g.) F.LHSV percent F. 210 \1 2, 500 760 1. 0 49. 3 0 20. 27 3. 96 100 2, 5007 1. 5 58. 4 N 24. 77 4. 46 99 2, 600 740 1. 0 66. 7 10 24. 76 4. 4O 931, 500 740 1. 0 71. 3 5 28.55 4. 65 80 1,500 7 1.0 70.4 10 25.80 4.46 ST1, 500 760 1. 5 T2. 1 +20 27. 84 4. 59 S0 1, 500 760 0. 5 43. 4 21. 654. 06 92 solution). The above solution was added to slurry of 60 clay inwater plus sodium silicate. Then was added 35 percent H,SO till pH was44.5. The acidified slurry was spray dried and the product was exchangedwith (NI-10 80 solution, then with NH OH solution. The

exchanged material was washed with water and flash 65 dried.

Theproduct is a powder with average particle size of about 64 microns.It has a packed density of 0.56 g/cc,

EXAMPLES 8-14 The procedure of Examples 1-7 was repeated with theexception that the ratio of cracking components was changed. In Examples8-13, the catalyst mixture contained 100 cubic centimeters of thenickeltungsten-silica-zirconia-clay and 20 cubic centimeters ofZnH/ZSM-S.

in Example 14 no conventional cracking component was present in thecatalyst so that .the catalyst was solely ZnH/ZSM-5. This example servesa control so as EXAMPLES 25 28 to show the improved results obtained bythe composite catalyst. Note the unacceptably low Viscosity lndex Theseexamples, taken with Examples 2931 u trate the effect of variedproportions ofthe two compo- Additional operating conditions and resultsare of the catalyst when Processing Stocks f y shown below: high pourpoint (high wax content). should be borne 650 F.+, Pour Pressure Temp.,wt. point, KV at KV at Example (p.s.i.g.) F. LHSV percen F. 100 210 VI49 +20 17.14 3. 70 112 1 i 67 +26 19.36 3.86 100 2, 500 740 1 61 +30 20..96 4. 16 111 1, 600 740 1 68 +20 22. 17 4. 1s 9s 1, 500 760 1 62 o 21.so 4. 14 100 1,600 760 0.5 40 -30 17.01 3.57 99 1, 500 740 0. 6 49 -1o22. 69 4. 20 95 500 700 16 7a a4. 18 4. 9s 66 EXAMPLES 15 19 20 1n mmdthat hydrocrackmg with conventional catalyst gives a net production ofwax by opening rings to high boiling straight or slightly branchedaliphatic compounds. For examples -28, the catalyst contained 100 partsof nickel-tungsten-silica-zirconia-clay and 20 The procedure of Examplesl-7 was repeated with the exception that a charge stock was used whichhad the following characteristics:

Gravity, API 23.2 25 parts of ZnH/ZSM-S. The charge stock had thefollow- Pour Point. ing properties: Sulfur, Wt. 2.07 -Wax',*Wt. 9.0

K.V-. 100F, cs 66.72 Gravity, API 23.8 K. V. 210F, cs 7.16 Pour Point,F. l20 Vacuum Assay, F Sulfur, wt.% 0.53 lBP 721 xv at ZIO'F. cs. 16.75% 778 Wax. wt.% 16.2

805 30 834 50% 846 Vacuum Assay (10 mm), "F 70% 871 mp 8 90% 893 5% 9s%I 916 10% 922 Analme point, i805 30% 940 I 957 Additional er 1' ditionsand r sults are Op a lng con 6 90% m2 shown below: 95% 1020 650 F. PourPressure Temp, t. point, KV at KV at Example (p.s.i.g.) F. LHSV percentF. 100 F. 210 F. VI

2,600 760 1. 0 62.8 0 30.13 4; 94 95 2,600 740 1.0 73. 16 39.85 6.66 851, 500 740 1. 0 80.8 10 46. 1s 6. 02 76 1, 600 760 1. 0 70.5 6 4o. 15 6.70 86 1, 500 760 1. 6 4s. 5 -1o 27. 69 4. 71 96 EXAMPLES 2024 Aftersolvent dewaxing, the stock had these characteristics: The procedure ofExamples 15-19 was repeated with the exception that the ratio ofcracking components 22,": i 20 25 20 1o I was changed. In Examples20-24, the catalyst mlxture Kv 8 3629, 3643 contained 100 cubiccentimeters of the nickel- Sulfur, wt.% 0.67

tungsten-silica-zirconia-clay and 20 cubic centimeters of ZnH/ZSM 5'Processing conditions with 8,000 SCF/B of hydrogen Additional operatingconditions and results are and results of processing are shown in thefollowing Tashown below: 6 ble:

650 F.+, Pour Pressure T0111p.. point. K\' at KV at Exmnplo (p.s.l.g.)F. LI'ISV percent F. 100 F. 1'10 F. \I

650 F Pressure Temp, wt Wax,wt Pour KV at KV at lfixmnplu (psig) F.LIISV percent percent pt., F. 100 F. 210 F. VI

25.. 2,500 760 1.0 85.3 5.3 Z2 12%;; 2g 20 2.500 760 0.5 70.0 5.3 l 98g:

,. 27 1,500 760 0.5 72.0 5.0 .fg g; 28 1, 500 760 1.0 87. 6 70 169. 213. 77 81 Hydrocrucked product solvent dewaxed to pour point indicated.

Example 25 was run at 2,500 psig, 760F, 1.0 LI-ISV, 8,000 SCF/Bhydrogen. The 650F+ product was obtained in 85.3 percent yield with 88V1. Removal of 5.3 percent wax brought the pour point down to F. Thisdemonstrates that the combination operation removed at least 1 1 percentwax (hydrocracking produces wax) and raised the VI by 20 units (the raw,dewaxed charge has a 65 VI). Similarly at 0.5 LI-ISV, the raw 650F+product was obtained in 70 percent yield with a +60F pour point (andpercent wax). After dewaxing, the hydrocracked oil had a 99 VI.

Examples 27 and 28 show that the operation is also feasible at 1,500psig where the yields are higher and the Vls are lower.

EXAMPLES 29-3l Using the same charge stock as shown for Examples 25-28,runs were made with a catalyst composite of 80 partsnickel-tungsten-silica-zirconia-clay at 8,000 SCF/B hydrogen. Furtherprocessing conditions and results obtained are shown in the followingtable:

b. a large pore cracking catalyst, and

c. a hydrogenation/dehydrogenation component in association with atleast one of catalysts (a) or (b) whereby the Viscosity Index and thePour Point of the oil are simultaneously enhanced.

2. The process of claim 1 wherein the large pore size aluminosilicate issynthetic faujasite.

3. The process of claim 1 wherein the ZSM-S type catalyst is ZSM-8.

4. The process of claim 1 wherein the ZSM-S type catalyst has been baseexchanged with hydrogen ions, ammonium ions, and mixtures thereof.

5. The process of claim 1 wherein the large pore cracking catalyst is aninorganic oxide.

6. The process of claim 5 wherein the inorganic oxide comprises silica.

7. The process of claim 1 wherein the large pore cracking catalyst is acrystalline aluminosilicate having a pore size from 6 to 15 Angstromunits.

8. The process for preparing low pour point lube oils which comprisescontacting a petroleum feed stock Pressure l.e1np., wt. Wax, wt. Pour KVat KV at Example (p.s.i.g.) F. LHSV percent percent pt., F. 100 F. 210F. VI

What is claimed is:

l. A process for preparing low pour point lube oils which comprisescontacting a petroleum charge stock having a boiling point above 650 F.and a low Viscosity Index under hydrocracking conditions to producelubricant of substantially higher Viscosity Index with a catalystcomposition comprising a mixture of a. a crystalline aluminosilicate ofthe ZSM-5 type having a composition in terms of mole ratios of oxides asfollows:

0.9 :t 0.2 M O A1 0 Y SiO, 2 11 0 wherein M is at least one cationhaving a valence n, Y is at least 5 and z is between 0 and 40, saidaluminosilicate having the x-ray diffraction lines as set forth in Table1 of the specification,

9. The process of claim 8 wherein M is a mixture of ammonium and zinccations.

* t t t mgg u STATES PATENT osmcs CERTFFICATE 0F GQECTEN mm No.3,755,1M5 Dated August 28, 1

BERNARD A. ORKIN- Inventofls) It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 6%, catalysti c" should be catalytic--. Column 2, line53, "of" should be --or--. Column 3, line 21, "to" shouldbe 2-5 --j-.

Column l, line, 58, "under a reaction" should be -under reaction--.5column L, line 61, "compositng" should be --compositing-.

Column 5, line 19, "an" should be --and--.; column 5, line 6-3, "stream"should be --steam--.5 column 5, line 65, "1500 1 "v should be --l500Fif--.

Column 6, line 1, "stream" should be --steam-- .5 column 6, line 17,"1:10 to 2:1" should be --l:lO up tov2:l--.

Column 7, lines 9-10, Delete "Compositions of this type includetechniques with" column 7, line 31 "to" should be --and--.

Signed and sealed this 5th day of February 1974.

(SEAL) Attest:

EDWARD MELETCHERJR. I RENE D. TEGTMEYER Attesting Officer ActingCommissioner of'Patem

2. The process of claim 1 wherein the large pore size aluminosilicate issynthetic faujasite.
 3. The process of claim 1 wherein the ZSM-5 typecatalyst is ZSM-8.
 4. The process of claim 1 wherein the ZSM-5 typecatalyst has been base exchanged with hydrogen ions, ammonium ions, andmixtures thereof.
 5. The process of claim 1 wherein the large porecracking catalyst is an inorganic oxide.
 6. The process of claim 5wherein the inorganic oxide comprises silica.
 7. The process of claim 1wherein the large pore cracking catalyst is a crystallinealuminosilicate having a pore size from 6 to 15 Angstrom units.
 8. Theprocess for preparing low pour point lube oils which comprisescontacting a petroleum feed stock having a boiling point above 650* F.under hydrocracking conditions with a catalyst composition comprising a.A ZSM-5 type zeolite having a composition in terms of mole ratios ofoxides as follows: 0.9 + or - 0.2 M2/nO : Al2O3 : Y SiO2 : z H2O whereinM is at least one cation having a valence n, Y is at least 5 and z isbetween 0 and 40, said aluminosilicate having the x-ray diffractionlines as set forth in Table 1 of the specification, and b. anickel-tungsten-silica-zirconia-clay cracking catalyst.
 9. The processof claim 8 wherein M is a mixture of ammonium and zinc cations.